75-46-7Relevant articles and documents
OXIDATIVE ADDITION OF SUBSTITUTED ARSINES AND STIBINES WITH BIS(TRIFLUOROMETHYL)NITROXYL
Ang, H. G.,Lien, W. S.
, p. 453 - 470 (1980)
Reactions of bis(trifluoromethyl)nitroxyl with a number of methyl- and trifluoromethyl- substituted arsines and stibines at room temperature lead to the formation of pentavalent arsenic and antimony derivatives, namely (CH3)3-n(CF3)nM2 (M = As, n = 0, 1, 2; M = Sb, n = 0, 1).The derivatives yield bis(trifluoromethyl)-hyroxylamine and the corresponding dichlorides on treatment with hydrogen chloride.A free radical mechanism is proposed for the oxidative addition reactions.
-
Coomber, J. W.,Whittle, E.
, p. 2183 - 2190 (1966)
-
Mixed-valence thiophosphorus compounds. Fluoro- and (trifluoromethyl)(thiophosphorylthio)phosphines with chiral phosphorus centers
Cavell, Ronald G.,Doty, Leon F.
, p. 3086 - 3093 (1978)
Reactions of the acids (CF3)2PS2H and F2PS2H with the fluoro(trifluoromethyl)aminophosphine CF3(F)PN(CH3)2 and the reaction of the new acid F(CF3)P(S)SH with the fluoro- or (trifluoromethyl)aminophosphines X2PN(CH3)2 (X = F, CF3) provide new isomeric (thiophosphorylthio)phosphines XYP(S)SPX′Y′ (X, Y, X′, Y′ = F, CF3) with chiral phosphorus centers. The compounds were characterized chemically and by NMR spectroscopy. Geminal CF3-CF3 (9.0 Hz for CF3 on pentavalent P; 7.2 Hz for CF3 on trivalent P) and F-F (82.5 Hz for F on pentavalent P; 92.5 Hz for F on trivalent P) coupling constants are revealed in the NMR spectra of the molecules as a result of the presence of the chiral phosphorus centers. Directly bound geminal fluorine atoms on trivalent P show large chemical shift difference between the two fluorine atoms (4.4 ppm) accompanied by substantially different 1JPF coupling constants (1370 and 1291 Hz). Similar but smaller differences prevail between geminal CF3 substituents. Reaction of the new acid F(CF3)P(S)SH with CF3(F)PN(CH3)2 gave a mixture of (thiophosphorylthio)phosphine isomers each with two chiral phosphorus centers. Only partial assignment of the major features of this spectrum could be made.
REACTIONS OF BIS(TRIFLUOROMETHYL)NITROXYL WITH CF3PX2 (WHERE X=F, Cl, Br, I AND CN) AND P(CN)3
ANG, H. G.,SO, K. K.
, p. 221 - 242 (1982)
The reactions between bis(trifluoromethyl)nitroxyl and CF3PX2 (where X=F, Cl, Br and CN) in 2:1 molar ratio give addition products, 2P(CF3)X2.The bromo and cyano products are unstable.The former decomposes at room temperature to give bromine and perfluoro-2-azapropene, and the latter yields predominantly (CF3)2NOCF3.With CF3PI2, iodine displacement occurs to afford 2PCF3.On the other hand, P(CN)3 affords 3PO, (CF3)2NON(CF3)2 and paracyanogen.Mechanisms for these reactions are proposed.
Non-Arrhenius Behaviour in the Reaction of CF3 Radicals with CH3CN and CD3CN
Pasteris, L.,Staricco, E. H.
, p. 1303 - 1310 (1985)
Evidence is presented that rate measurements over a wide temperature range, 298-648 K, for the reaction of CF3 radicals with methyl cyanide show non-Arrhenius behaviour when the photolysis of trifluoromethyl iodide is used as a source radicals.The results presented here support the fact that the curved Arrhenius plot may be explained in terms of two reaction channels giving the same product, CF3H.One is the abstraction by the CF3 radicals and the other involves the iodine atom produced in the photolysis of CF3I.In order to obtain further information on the reaction mechanism the kinetic isotope effect has also been studied.
Emeleus, H. J.,Haszeldine, R. N.,Paul, R. C.
, (1954)
The gas-phase reaction of the CF3 radical with thiophene
Herrera, Olga S.,Nieto, Jorge D.,Lane, Silvia I.,Oexler, Elena V.
, p. 1477 - 1481 (2003)
The reaction of CF3 radicals, generated by photolysis of CF 3I or hexafluoroacetone with thiophene, was studied in the gas phase at 25°C. At conversion of thiophene less than 20%, monosubstituted CF 3-thiophenes were found as the main reaction products, in addition to CF3H, C2F6, and monosubstituted dihydro-CF3-thiophene, the latter in very low proportion. An isomeric mixture of 2- and 3-CF3-thiophene was obtained in a ratio of about 16, independent of the radical source used (CF3I or hexafluoroacetone) to produce the CF3 radicals. A plausible mechanism that accounts for the observed products is proposed, and the reactivity of thiophene toward the CF3 radical at 25°C was determined as kadd/kc1/2 = 106 ± 4 cm3/2 mol-1/2 s-1/2.
-
Fevre, H. F. Le,Timmons, R. B.
, p. 3854 - 3859 (1969)
-
Conversion of CFC-13 to trifluoroacetic acid by electrochemical reaction with carbon dioxide
Sonoyama, Noriyuki,Sakata, Tadayoshi
, p. 444 - 445 (2002)
The electrochemical conversion of CFC-13 (CClF3) and carbon dioxide into trifluoroacetic acid (TFAA) was attempted at a Ag wire electrode under high pressure. TFAA was efficiently produced and the current efficiency was slightly dependent on the potential during electrolysis and pressure of co-existing carbon dioxide.
-
Ayscough et al.
, p. 743,744 (1955)
-
Experimental Measurement of the Electron Affinity of the Hydroperoxy Radical
Bierbaum, Veronica M.,Schmitt, Robert J.,DePuy, Charles H.,Mead, Roy D.,Schulz, P. A.,Lineberger, W. C.
, p. 6262 - 6263 (1981)
-
Evaluation of the kinetic parameters for the reaction of trifluoromethyl radicals with CH3Cl in the gas phase in temperature range from 416 to 63 K
Taccone,Olleta,Salinovich
, p. 353 - 362 (1993)
The hydrogen and chlorine atom abstraction reactions from CH3Cl by CF3 radicals produced by the photolysis of hexafluoroacetone (HFA) and CF3I were studied relative to the recombination of CF3 radicals:
Mechanistic study of nucleophilic fluorination for the synthesis of fluorine-18 labeled fluoroform with high molar activity fromN-difluoromethyltriazolium triflate
Chai, Jin Young,Cha, Hyojin,Lee, Sung-Sik,Oh, Young-Ho,Lee, Sungyul,Chi, Dae Yoon
, p. 6099 - 6106 (2021/02/12)
The synthesis of fluorine-18 labeled fluoroform with high molar activity has grown in importance for the development of fluorine-18 labeled aryl-CF3radiopharmaceuticals that are useful as diagnostic radiotracers for the powerful technique of positron emission tomography (PET). We designed a strategy of synthesizing fluorine-18 labeled fluoroform fromN1-difluoromethyl-N3-methyltriazolium triflate (1)viaSN2 fluorination without stable fluorine isotope scrambling. Fluoroform was generated at rt in 10 min by fluorination of the triazolium precursor with TBAF (6 equiv.). We propose three routes (a), (b), and (c) for this fluorination. Quantum chemical calculations have been carried out to elucidate the mechanism of experimentally observed nucleophilic attack of fluoride at difluoromethyl groupviaroute (a), notN3-methylviaroute (b).1H and19F NMR studies using deuterium source have been performed to examine the competition between SN2 fluorination (route (a)) and the formation of difluorocarbene (route (c)). The observed superiority of SN2 pathway to formation of difluorocarbene in the reaction of the precursor using CsF in (CD3CN/(CD3)3COD (17.8?:?1)) gives the possibility of preparing the fluorine-18 labeled fluoroform in high molar activity.
PROCESSES FOR PRODUCING TRIFLUOROIODOMETHANE USING METAL TRIFLUOROACETATES
-
Paragraph 0025-0030, (2020/09/19)
The present disclosure provides a process for producing trifluoroiodomethane. The process includes providing a metal trifluoroacetate, iodine, a phase transfer catalyst, and an organic solvent, and reacting the metal trifluoroacetate and iodine in the presence of the phase transfer catalyst and the organic solvent to produce trifluoroiodomethane.
